JPS5914067B2 - Vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in vinyl chloride resin compositions, particularly to vinyl chloride copolymer resin compositions in which both impact strength and hot moldability are significantly improved.

5 Conventionally, vinyl chloride homopolymers (hereinafter referred to as hard P
It's called VC.

) is used in various applications such as records, sheets, bottles, corrugated plates, and pipes, but it is hardly used in home appliances, automobile parts, etc. because of its insufficient impact resistance. Although ABS'o resin, polycarbonate resin, etc. have high impact strength, they have low flame retardancy, so they are difficult to put into practical use for the above-mentioned purposes. Copolymer resins of vinyl chloride and α-olefins have high melt fluidity and are known as improved vinyl chloride resins, but they still do not have sufficient impact resistance. As a method to improve the impact resistance of rigid PVC,
A method of mixing methyl methacrylate, butadiene and styrene copolymer resin (hereinafter referred to as MBS resin) containing a rubber component, chlorinated polyethylene, etc., and a method of mixing fibrous substances such as asbestos, glass fiber, etc. Although this method is known, if these reinforcing agents or fibrous substances are mixed with hard PVC, the melt flowability and hot formability are not improved, so there is a limit to the shape of the product that can be molded, and simple shapes are not possible. It was limited to molded products. ■5 The present inventors created a resin paraboloid by blending the above MBS resin with a commonly used α-olefin and vinyl chloride copolymer with a polymerization degree of 800 or less, which has high melt flowability, and tested the performance. However, it was found that neither the impact resistance nor the hot formability improved significantly30. However, in addition to this, the degree of polymerization is 80
A composition obtained by blending the above MBS resin and methyl methacrylate copolymer in a specific ratio with an α-olefin and vinyl chloride copolymer resin having a molecular weight of more than 850, particularly 850 or more, has excellent impact resistance and heat resistance. It was found that the moldability of both samples 35 and 35 was significantly high. The term "hot formability" refers to the formability in vacuum forming, etc. at a temperature of around 100°C.
It is evaluated that the higher the tensile elongation rate at °C, the better the hot formability. The object of the present invention is to provide a vinyl chloride copolymer resin composition which has excellent flame retardancy, hardness, weather resistance, chemical resistance and heat resistance, and in particular has significantly improved impact strength and hot formability. It is about providing. In particular, the resin composition targeted by the present invention has Izod impact strength (JISK-7
According to the method of No. 110. ) is 60Kf-CTfL/d or more, the tensile strength at 100℃ (ASTMD-6
The elongation rate at 100°C is 1310% or more, and the heat distortion temperature (ASTMD-
According to the method of 648. ) indicates a value of 70°C or higher. The vinyl chloride copolymer resin composition of the present invention has an average degree of polymerization of 850 to 2000, and has ethylene,
0.3 to 10 mol% of one or more α-olefins selected from the group consisting of propylene and 1-butene
and 100 parts by weight of a vinyl chloride copolymer consisting of 90 to 99.7 mol% of vinyl chloride, 11 to 28 parts by weight of a methyl methacrylate-butadiene-styrene ternary copolymer resin, and 55 to 90 parts by weight of methyl methacrylate. It is characterized by containing 0.4 to 14 parts by weight of a methyl methacrylate copolymer comprising 10 to 45% by weight of a copolymerizable component. The vinyl chloride copolymer used in the present invention can be easily produced by a conventional suspension polymerization method of α-olefin such as ethylene, propylene, 1-butene, etc. and vinyl chloride. The amount of olefin and the average degree of polymerization of the copolymer are specific.

If the amount of the α-olefin in the copolymer is 0.3 mol% or less, the copolymer will have poor melt fluidity, and it will not be possible to melt-knead it with other components used in the resin composition of the present invention and form it into a sheet. In addition, if the amount of α-olefin is 10 mol % or more, the heat distortion temperature of the copolymer decreases, and the composition with other components used in the resin composition of the present invention decreases. does not exhibit sufficient heat resistance. Furthermore, even if α-olefin and vinyl chloride are copolymerized in the above ratio, if the average degree of polymerization of the copolymer is less than 850, particularly less than 800, the copolymer will have poor tensile strength and elongation at high temperatures. The resin composition of the combination and other components used in the resin composition of the present invention does not exhibit sufficient heat resistance. However, when the average degree of polymerization is 2,000 or more, the melt fluidity of the copolymer decreases significantly, and the moldability of a resin composition using the copolymer becomes insufficient. Thus, the preferred copolymer of the α-olefin and vinyl chloride used in the present invention is α-olefin and vinyl chloride.
- The amount of olefin is limited to 0.3 to 10 mol % and the average degree of polymerization is 850 to 2000. The methyl methacrylate butadiene-styrene terpolymer resin used in the present invention is conventionally known as an MBS resin impact strength improver.

Particularly preferred is a butadiene-styrene copolymer graft-copolymerized with methyl methacrylate. Usually, a small amount of a crosslinking component is copolymerized with the methyl methacrylate-butadiene-styrene terpolymer, but one that does not contain this can also be used in the present invention. The component composition of the ternary copolymer resin used in the present invention is 3 to 30% by weight of methyl methacrylate, 25 to 60% by weight of butadiene, and 15 to 4% of styrene.
A ratio of 0% by weight and a crosslinking component of 5% or less is preferable. Examples of the above-mentioned crosslinking components include divinylbenzene, trivinylbenzene, divinyltoluene, dimethacrylic acid ester or diacrylic acid ester of mono-, di-, or triethylene glycol, diacrylic acid ester or dimethacrylic acid ester of 1.3-butanediol, etc. can be mentioned.

The methyl methacrylate copolymer used in the present invention is conventionally known as a molding processing aid, but it contains 55 to 90% by weight of methyl methacrylate and other components that can be copolymerized with methyl methacrylate. 10-45
Copolymers with % by weight are preferred.

Examples of the other copolymer components include acrylic acid esters such as methyl acrylate and ethyl acrylate, styrene, divinylbenzene, and the like. A particularly preferred methyl methacrylate copolymer is 0.19/100
The 25°C reduced viscosity of m1 chloroform solution is 1.2 or more. The resin composition of the present invention comprises 100 parts by weight of the vinyl chloride copolymer, 11 to 28 parts by weight of the methyl methacrylate-butadiene-styrene ternary copolymer resin, and 0.4 to 0.4 parts by weight of the methyl methacrylate copolymer.
14 parts by weight.

If the content of the terpolymer resin is lower than 11 parts by weight, the impact strength of the resin composition will decrease, and if it is 28 parts by weight or more, the tensile strength at heat distortion temperature and high temperature will be significant. The flame retardancy also deteriorates. If the content of the methyl methacrylate copolymer is less than 0.4 parts by weight, the resin composition will not have sufficient tensile elongation at high temperatures, and if it is 14 parts by weight or more, the impact strength of the resin composition will be insufficient. This results in poor flame retardancy. The resin composition of the present invention may of course contain various additives used in combination during the molding process of polyvinyl chloride resin, as long as the object of the present invention is achieved.

Examples of these include stabilizers such as calcium stearate, zinc stearate, dioctyltibis-2-ethylhexylthioacetate, octyltin maleate, lubricants such as stearic acid, polyethylene wax, glycerin monostearate, calcium carbonate, gypsum, and talc. fillers such as titanium oxide, pigments such as carbon black, chelating agents such as trinonyl phenyl phosphorite, antioxidants such as butylated hydroxytoluene, ultraviolet absorbers such as hydroxybenzophenone, zorbitan fatty acid esters, etc. Examples include antistatic agents. The resin composition of the present invention is easily prepared by a conventional mixing method, such as a powder mixing method, a melt kneading method, etc., that is, using a powder mixer, an extruder, a roll kneader, etc. The composition of the present invention is widely used as an industrial material for various purposes, and since it has particularly good hot formability, it is useful for producing molded articles with complex shapes by vacuum forming. A more detailed explanation will be given below with reference to Examples and Comparative Examples, and the performance test of the resin composition was conducted in the following manner.

Further, polyvinyl chloride and a copolymer of vinyl chloride and α-olefin were produced by a suspension polymerization method, and the resulting polymers are shown in Table 1. Test method (1) Vinyl chloride and α-
Average degree of polymerization (P) of olefin copolymer resin; JISK
-6721 (2) α-olefin content (mol%);
; According to the Carius method.

(3) Solution viscosity: Sample 0.19 was dissolved in 100 cc of chloroform and measured at 25°C.

(4) Heat distortion temperature; according to ASTM-D-648.

(5) Melt viscosity: 17n by Koka type flow tester
&φ×10m1 nozzle at 180℃, load 150
Based on the apparent melt viscosity measured under the conditions of Kf. (6) Impact strength: Based on Izot impact test according to JISK-7110.

(7) Flammability: Evaluation of flame retardancy and measurement of combustion time according to UL Standard 94.

(8) Tensile strength and elongation; measured at 100°C using a constant temperature bath according to ASTM D-638.

(9) Chemical resistance; according to JISK-6745.

Example 1 Vinyl chloride copolymer 100 of C shown in Table 1
In the weight part, commercially available methyl methacrylate-butadiene-styrene ternary copolymer resin P (manufactured by Mitsubishi Rayon Co., Ltd.)
18 parts by weight of methyl methacrylate copolymer
A mixture of 4 parts by weight of m1 chloroform solution (25°C reduced viscosity of 3.5), 4 parts by weight of dioctylthibbis-2-ethylhexylthioacetate as a stabilizer, and 1 part by weight of stearyl alcohol as a lubricant was added to the surface. The resin composition of the present invention was obtained by kneading for 5 minutes using a 6-inch roll at a temperature of 185°C.

Next, a plate was molded from the above composition by compression molding using a 50-ton hot press machine, and test pieces for each of the above tests were prepared from this plate, and performance tests were conducted. Shown in the table.

It can be seen that the resin composition has excellent performance. Example 2
~7 Example 1 except that the copolymer D or F shown in Table 1 was used instead of the vinyl chloride copolymer C in Example 1, and the resin composition was blended in the amount shown in Table 2. Similarly, a resin composition was prepared, a plate was molded, and a performance test was conducted, and the results shown in Table 2 were obtained.

All have shown excellent performance. In addition, the above Example 1
The results of 7 to 7 show that the tensile elongation at 10'C tends to decrease as the content of α-olefin and the average degree of polymerization of the vinyl chloride copolymer decrease. Comparative Examples 1 to 12 As vinyl chloride copolymers, A, B, D, E, and F shown in Table 1 were used as methyl methacrylate-butadiene-styrene ternary copolymer resins, and the above cloth product P and further commercially available products were used. Q(
Manufactured by Mitsubishi Rayon Co., Ltd., product name Metablane C-102)
In addition, as a methyl methacrylate copolymer, the above-mentioned cloth product Preparation of a resin composition in the same manner as in Example 1, except that the same stabilizers and lubricants were used as those used in Example 1, and the resin composition was blended with the resin composition shown in Table 2. The plate was molded and performance tested, and the results shown in Table 2 were obtained.

Claims (1)

[Claims] 1 One or more α-olefins having an average degree of polymerization of 850 to 2000 and selected from the group consisting of ethylene, propylene, and 1-butene 0.3-10
100 parts by weight of a vinyl chloride copolymer consisting of 90 to 99.7 mol% of vinyl chloride, 11 to 28 parts by weight of a methyl methacrylate-butadiene-styrene ternary copolymer resin, and 55 to 90 parts by weight of methyl methacrylate. A vinyl chloride copolymer resin composition comprising 0.4 to 14 parts by weight of a methyl methacrylate copolymer comprising 10 to 45 weight % of a copolymer component that can be copolymerized with the vinyl chloride copolymer resin composition.